X-Ray Scintillators, Metal Halide Hybrids, Devices, and Methods

ABSTRACT

Methods of scintillation, scintillation devices, and metal halide hybrids that may be used as X-ray scintillators. The metal halide hybrids may include organic metal halide hybrids, inorganic metal halide hybrids, or organic-inorganic metal halide hybrids. The metal halide hybrids may have a 0D structure. The metal halide hybrids may be in the form of one or more discrete crystals.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims priority to U.S. Provisional Patent ApplicationNo. 62/989,015, filed Mar. 13, 2020, which is incorporated herein byreference.

STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT

This invention was made with government support under contract no.1709116 awarded by the National Science Foundation, and contract no.17RT0906 awarded by the Air Force Office of Scientific Research. Thegovernment has certain rights in this invention.

BACKGROUND

Scintillators are utilized for X-ray detection in many important fields,e.g., homeland security, health care, etc. Scintillators have theability to convert ionizing radiation into visible photons, and can beused as radiation detectors for radiation exposure monitoring, securityinspection, space exploration, and medical imaging.

X-ray scintillators are scintillation-based indirect detectors, whichabsorb and down convert high-energy ionizing radiation intoultraviolet-visible light for detection of X-rays. As compared to directX-ray detectors that convert X-ray to electric current, scintillatorscan have numerous advantages, such as high response rates, largeabsorption cross section, and/or high stability.

While various types of materials have been used for X-ray scintillators,there are still many disadvantages associated with existing organic andinorganic scintillation materials. For example, existing organic andinorganic scintillation materials can require rigorous preparationconditions. Other disadvantages include their hygroscopicity,anisotropic scintillation of organic crystals, low light yields inplastics, etc. Most commercially available scintillators are based oninorganic single crystals, which are prepared via time-consuming hightemperature processes, which typically must be performed under vacuum.Current scintillators include inorganic crystals, such as CsI(TI),CsI(Na), CdWO4, YAG(Ce), and LYSO, which typically requirehigh-temperature synthesis techniques, are hygroscopic, or a combinationthereof.

To reduce the energy consumption for material preparation, many organicscintillators have been developed with low temperature processes. Thesematerials, however, typically exhibit inferior performance (e.g., lowerscintillation light yields and/or resolutions) compared to inorganicscintillators.

Organic-inorganic metal halide perovskites and perovskite-relatedhybrids have a number of possibly valuable characteristics, such asexcellent luminescence properties, high absorption coefficients forionizing radiation, and solution-process preparations. For instance,methylammonium (MA) lead halide perovskite crystals, MAPbI₃ and MAPbBr₃,have displayed a light yield of around 1000 photons per MeV (ph MeV⁻¹).All inorganic CsPbBr₃ nanocrystals have been used to fabricatescintillating panels with good X-ray imaging (see, e.g., Chen, Q. S. etal. Nature 2018, 561, 88-93). Another organic lead halide hybrid(EDBE)PbCl₄ (EDBE=2,2′-(ethylenedioxy)bis(ethylammonium) cation) wasreported to have a light yield of ˜9000 ph MeV⁻¹ at room temperature(see, e.g., Birowosuto, M. D. et al. Sci. Rep. 2016, 6, 37254). Whilegreat potential has been shown in these materials, their use in manyapplications is still limited by the low long-term stability and leadtoxicity.

Lead-free low-dimensional metal halide hybrids have been developed toexhibit high luminescence and excellent stability, which make themhighly attractive for X-ray scintillators. For example, a lead-free 1Dstructure Rb₂CuBr₃ scintillator has been reported, which has a highlight yield (˜91000 ph MeV⁻¹) and good spectral stability for two monthsunder ambient conditions (Yang, B. et al. Adv. Mater. 2019, 31,1904711). A zero-dimensional (0D) Bmpip₂SnBr₄(Bmpip=1-butyl-1-methyl-piperidinium cation) based scintillator hasexhibited a higher scintillation light yield than that of NaI:TI (Morad,V. et al. J. Am. Chem. Soc. 2019, 141, 9764-9768). However, the PLQE(75%) of this material is still not optimal and the easy oxidation of Sn(II) to Sn (IV) makes the material unstable.

Therefore, there remains a need for metal halide hybrids, includinghighly stable luminescent 0D metal halide hybrids, for scintillators,such as metal halide hybrids that exhibit high light yield and/orstability upon irradiation with high-energy radiation. There alsoremains a need for scintillation materials, including materials that canbe synthesized relatively inexpensively, are eco-friendly (e.g.,lead-free, heavy metal-free, etc.), have a high quality crystalstructure (e.g., relatively large in size, stable, etc.), have a strongvisible emission with high photoluminescence quantum efficiency (PLQE),exhibit a greater light yield than most conventional commerciallyavailable scintillators, or a combination thereof.

BRIEF SUMMARY

Provided herein are metal halide hybrids, including 0D metal halidehybrids, that may be used as scintillation materials. The metal halidehybrids provided herein, in some embodiments, are stable, relativelyeasy to synthesize, eco-friendly, and/or exhibit a desirable lightyield, including light yields that exceed many commercially availablescintillators. Also provided herein are methods for scintillation anddevices.

In one aspect, methods for scintillation are provided. The methods forscintillation, in some embodiments, include irradiating a metal halidehybrid with high-energy radiation to convert the high-energy radiationto at least one of near ultraviolet light or visible light. The metalhalide hybrid may have a 0D structure. The high-energy radiation mayinclude X-rays, gamma rays, or a combination thereof. In someembodiments, the methods include irradiating a metal halide hybrid withX-rays at a dose rate of about 10 microGy/s to about 40 microGy/s.

In another aspect, devices, including scintillation devices, areprovided. In some embodiments, the methods include a scintillatorscreen. The scintillator screen may include a metal halide hybrid. Insome embodiments, the scintillation devices also include one or more of

an electronic substrate, an imaging chip, or a fiber-optic face plate.In some embodiments, the metal halide hybrid has a 0D structure. In someembodiments, the scintillation devices also include a housing in whichone or more components of the scintillation devices are arranged. Insome embodiments, the imaging chip comprises a complementary metal oxidesemiconductor image sensor.

In yet another aspect, metal halide hybrids are provided. In someembodiments, the metal halide hybrids include an organic antimonyhalide. The organic antimony halide may include a crystal according toFormula (I)—

R₂SbX₅  Formula (I),

wherein X is a halide, and wherein R is an organic ammonium cation. Insome embodiments, the metal halide hybrids include an organic manganese(II) halide hybrid. The organic manganese (II) halide hybrid may includea crystal according to Formula (III)—

R′MnX₄  Formula (III),

wherein X is a halide, and R′ is an organic phosphonium cation. In someembodiments, the metal halide hybrids provided herein have a first PLQEmeasured within one week of the metal halide hybrid's creation, a secondPLQE measured after the metal halide hybrid is stored at ambientconditions for at least one year following the metal halide hybrid'screation, and the second PLQE is no more than 3 percentage points lessthan the first PLQE.

In a still further aspect, scintillation materials are provided herein.The scintillation materials may include a metal halide hybrid. Thescintillation materials may include a flexible film.

Other objects, features, and advantages of the invention will beapparent from the following detailed description, drawings, and claims.Unless otherwise defined, all technical and scientific terms andabbreviations used herein have the same meaning as commonly understoodby one of ordinary skill in the art to which this invention pertains.Although methods and compositions similar or equivalent to thosedescribed herein can be used in the practice of the present invention,suitable methods and compositions are described without intending thatany such methods and compositions limit the invention herein.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1A is a schematic of an embodiment of a scintillator device.

FIG. 1B is a cross-sectional view of the scintillator device of FIG. 1A.

FIG. 2 depicts the absorption, excitation, and emission spectra of anembodiment of a metal halide hybrid.

FIG. 3 depicts the photoluminescence intensity of an embodiment of ametal halide hybrid at various times from 0 to 32 days.

FIG. 4A depicts excitation and emission spectra of an embodiment of ametal halide hybrid.

FIG. 4B depicts emission spectra of an embodiment of a metal halidehybrid at 300 nm.

FIG. 5A depicts a comparison of scintillator light yields of anembodiment of a metal halide hybrid and commercially availablescintillators.

FIG. 5B depicts a plot of the change in intensity observed for anembodiment of a metal halide hybrid under continuous X-ray excitation ata dose rate of 26 microGy/s.

FIG. 6A depicts excitation and emission spectra of an embodiment of ametal halide hybrid.

FIG. 6B depicts time resolved photoluminescence spectra of an embodimentof a metal halide hybrid.

FIG. 6C depicts time resolved photoluminescence spectra of an embodimentof a metal halide hybrid.

FIG. 7 depicts photoluminescence spectra for an embodiment of a metalhalide hybrid.

FIG. 8A depicts a random laser spectra of an embodiment of a metalhalide hybrid.

FIG. 8B depicts the relationship between X-ray dose rate and randomlaser intensity for an embodiment of a metal halide hybrid.

FIG. 8C depicts the relationship between X-ray dose rate and randomlaser intensity for an embodiment of a metal halide hybrid.

FIG. 8D depicts a comparison of scintillation light yields of anembodiment of a metal halide hybrid and commercially availablescintillators.

FIG. 8E depicts random laser intensities of an embodiment of a metalhalide hybrid at various times from 0 to 180 minutes.

FIG. 9A depicts the intensities of an embodiment of a metal halidehybrid at 0 and 2 years.

FIG. 9B depicts a thermogravimetric analysis of an embodiment of a metalhalide hybrid.

DETAILED DESCRIPTION

Provided herein are metal halide hybrids, and methods for scintillationand scintillation devices that may include a metal halide hybrid.

Methods for Scintillation

Provided herein are methods for scintillation. In some embodiments, themethods include irradiating a metal halide hybrid with high-energyradiation to convert the high-energy radiation to at least one of nearultraviolet light or visible light. In other words, the high-energyradiation may be converted to near ultraviolet light, visible light, ora combination thereof.

In some embodiments, the high-energy radiation includes X-rays, gammarays, or a combination thereof. In some embodiments, the high-energyradiation consists of X-rays.

A metal halide hybrid may be irradiated with high-energy radiation atany dose rate. In some embodiments, a metal halide hybrid is irradiatedwith high-energy radiation, such as X-rays, at a dose rate of about 5microGy/s to about 100 microGy/s, about 5 microGy/s to about 80microGy/s, about 10 microGy/s to about 60 microGy/s, or about 10microGy/s to about 40 microGy/s.

A metal halide hybrid may exhibit a light yield suitable for manyapplications. In some embodiments, a metal halide hybrid exhibits alight yield of at least 50,000 photons/MeV, at least 60,000 photons/MeV,at least 70,000 photons/MeV, at least 80,000 photons/MeV, or at least90,000 photos/MeV.

A metal halide hybrid may exhibit a suitable detection limit. In someembodiments, a metal halide hybrid exhibits a detection limit of about50 nGy/s to about 500 nGy/s, about 50 nGy/s to about 400 nGy/s, about 50nGy/s to about 300 nGy/s, about 50 nGy/s to about 200 nGy/s, about 60nGy/s to about 90 nGy/s, or about 65 nGy/s to about 85 nGy/s.

Scintillation Devices

Scintillation devices also are provided herein. In some embodiments, thescintillation devices include a scintillator screen that includes ametal halide hybrid. A scintillator screen “includes” or “comprises” ametal halide hybrid when the metal halide hybrid is disposed on and/ordispersed in the scintillator screen. In some embodiments, thescintillation devices include a scintillator screen and one or more ofthe following components: an electronic substrate, an imaging chip, anda fiber-optic face plate.

In some embodiments, the scintillation devices include an electronicsubstrate; an imaging chip; a fiber-optic face plate, wherein theimaging chip is arranged between the electronic substrate and thefiber-optic face plate; and a scintillator screen including a metalhalide hybrid, wherein the fiber-optic face plate is arranged betweenthe imaging chip and the scintillator screen.

The scintillation devices also may include a housing. One or morecomponents of the scintillation devices may be arranged in the housing.A component is “arranged in a housing” when all or a portion of thecomponent is at least partially encased by the housing. The housing maybe formed of any suitable material(s).

Schematics of an embodiment of a scintillation device are depicted atFIG. 1A and FIG. 1B. The scintillation device 100 includes a housing110. Within the housing 110, the scintillation device 100 includes ascintillator screen 120, a fiber-optic face plate 130, an imaging chip140, and an electronic substrate 150. When the scintillation device 100is used, the device may be oriented so that high-energy radiation 160contacts the scintillation device 100 in the direction shown.

In some embodiments, the imaging chip includes a complementary metaloxide semiconductor image sensor.

In some embodiments, the metal halide hybrid is in the form of one ormore discrete crystals dispersed in and/or arranged on a scintillatorscreen. In some embodiments, the scintillator screen includes a film,such as a flexible film, as described herein.

Metal Halide Hybrids

Metal halide hybrids are provided herein, including metal halide hybridsthat may be used in the methods and/or devices provided herein.

As used herein, the phrase “metal halide hybrid” refers to a compound,such as a crystal, having a formula (e.g., a unit cell formula) thatincludes one or more metal atoms, one or more halide atoms, and one ormore cations. The one or more metal atoms may be the same or different;the one or more halide atoms may the same or different (e.g., a metalmixed halide hybrid); and the one or more cations may be the same ordifferent (e.g., an organic-inorganic metal halide hybrid).

In some embodiments, the metal halide hybrid is an organic metal halidehybrid. As used herein, the phrase “organic metal halide hybrid” refersto a metal halide hybrid that includes one or more organic cations(e.g., an organic ammonium cation), and the one or more organic cationsmay be the same or different. An “organic cation” is a cation thatincludes at least one carbon atom, at least one hydrogen atom, and atleast one positively charged atom (for example, a positively chargednitrogen atom). In some embodiments, the organic metal halide hybrid isan organic metal mixed halide hybrid, which includes two or moredifferent halide atoms (e.g., Cl⁻ and Br⁻; or Br⁻ and I⁻; etc.).

In some embodiments, the metal halide hybrid is an inorganic metalhalide hybrid. As used herein, the phrase “inorganic metal halidehybrid” refers to a metal halide hybrid that includes one or moreinorganic cations (e.g., a cesium atom), and the one or more inorganiccations may be the same or different. An “inorganic cation” is a cationthat includes a positively charged atom, and does not include a carbonatom. In some embodiments, the inorganic metal halide hybrid is aninorganic metal mixed halide hybrid, which includes two or moredifferent halide atoms (e.g., Cl⁻ and Br; or Br⁻ and I⁻; etc.).

In some embodiments, the metal halide hybrid is an organic-inorganicmetal halide hybrid. As used herein, the phrase “organic-inorganic metalhalide hybrid” refers to a metal halide hybrid that includes at leastone organic cation (e.g., an organic ammonium cation) and at least oneinorganic cation (e.g., a cesium atom), and the one or more organiccations may be the same or different, and the one or more inorganiccations may be the same or different. In some embodiments, theorganic-inorganic metal halide hybrid includes an organic-inorganicmetal mixed halide hybrid, which includes two or more different halideatoms (e.g., Cl⁻ and Br⁻; or Br⁻ and I⁻; etc.).

The metal halide hybrid may have any crystal structure. In someembodiments, the metal halide hybrid has a 0D structure. In someembodiments, the metal halide hybrid has a 1D structure. In someembodiments, the metal halide hybrid has a 2D structure. In someembodiments, the metal halide hybrid has a 3D structure.

In some embodiments, the metal halide hybrid includes one or more metalsselected from Sn, In, Sb, Bi, Mn, Hg, Zn, Ge, or a combination thereof.

The halide of a metal halide hybrid may include F⁻, Cl⁻, Br⁻, I⁻, or acombination thereof.

The metal halide hybrids may include any inorganic cation. In someembodiments, the inorganic cation includes a cesium atom.

The metal halide hybrids may include any organic cation. In someembodiments, the organic cation includes an organic ammonium cation, anorganic phosphonium cation, or a combination thereof. Non-limitingexamples of organic cations that may appear in the metal halide hybridsherein include those of Formula (IIa), Formula (IIb), and Formula (IV)described herein.

The metal halide hybrids described herein may be in any physicalform(s). For example, the metal halide hybrids irradiated withhigh-energy radiation in the methods described herein and/or the metalhalide hybrids included in the scintillator screens of the devicesdescribed herein may be in any physical form(s).

In some embodiments, the metal halide hybrid is in the form of one ormore discrete crystals. The one or more discrete crystals may be of anysize. In some embodiments, the crystals include one or more singlecrystals having a largest dimension of about 1 mm to about 30 mm, about1 mm to about 20 mm, about 1 mm to about 15 mm or about 1 mm to about 10mm. In some embodiments, the metal halide hybrid is in the form of apowder (i.e., a plurality of particles having an average largestdimension less than 1 mm).

The metal halide hybrid may be dispersed in a matrix material. The metalhalide hybrid, for example, may be dispersed evenly or unevenly in amatrix material. The matrix material may include one or more polymers,such as polydimethylsiloxane. The matrix material in which the metalhalide particles are dispersed may be in the form of a film. The filmmay be a flexible film. The film, in some embodiments, is a polymericthree-dimensional microstructured film. Any of the films describedherein may be used as a scintillator screen in the devices herein.

The metal halide hybrids may be relatively stable. For example, a metalhalide hybrid may have (i) a first PLQE measured within one week of themetal halide hybrid's creation, (ii) a second PLQE measured after themetal halide hybrid is stored at ambient conditions for at least oneyear or at least two years following the metal halide hybrid's creation,and (iii) the second PLQE is no more than 3 percentage points, 2percentage points, or 1 percentage point less than the first PLQE.

In some embodiments, the metal halide perovskite has a PLQE of at least95%, at least 96%, at least 97%, at least 98%, or at least 99%.

Non-limiting examples of metal halide hybrids that may be used in themethods and devices disclosed herein are listed at the following table:

Embodiment of Metal Halide Hybrid Reference (C₄N₂H₁₄Br)₄SnBr₆ Zhou, C.,Chem. Sci. 2018, 9, 586. (C₄N₂H₁₄I)₄SnI₆ Zhou, C., Chem. Sci. 2018, 9,586. (C₄H₁₄N₂)₂In₂Br₁₀ Zhou, L. Angew. Chem., Int. Ed. 2019, 58, 15435.(C₆H₅CH₂NH₃)₃InBr₆ Chen, D. J. Mater. Chem. C 2020, 8, 7322.(C₆H₅CH₂NH₃)₃SbBr₆ Chen, D. J. Mater. Chem. C 2020, 8, 7322.(C₆H₅CH₂NH₃)₃BiBr₆ Chen, D. J. Mater. Chem. C 2020, 8, 7322.(C₆H₈N₂O₂)₃SbBr₆ Lin, F. J. Mater. Chem. C 2020, 8, 7300.(C₆N₂H₁₆Cl)₂SnCl₆ Song. G. et al. J. Phys. Chem. Lett. 2020, 11, 1808.[(C₈H₁₂N)₄SnBr₆][(C₈H₁₂N)Br]₂[CCl₂H₂]₂ Xu, L. J. et al. Chem. Mater.2020, 32, 4692. (C₂₄H₂₀P)₂SbCl₅ Zhou, C. et al. Chem. Mater. 2018, 30,2374. (C₂₄H₂₀P)₂MnBr₄ Xu, L. J. et al. Adv. Mater. 2017, 29, 1605739.(C₁₁H₁₃N₂)₂SbCl₅ Wang, Z. et al. Angew. Chem., Int. Ed. 2019, 58, 9974.(C₁₁H₁₃N₂)₃SbCl₆ Wang, Z. et al. Angew. Chem., Int. Ed. 2019, 58, 9974.(C₅H₇N₂)₂HgBr₄•H₂O Yangui, A. et al. Chem. Mater. 2019, 31, 2983.(C₅H₇N₂)₂ZnBr₄ Yangui, A. et al. Chem. Mater. 2019, 31, 2983.(C₉NH₂₀)₂SnBr₄ Zhou, C. et al. Angew. Chem., Int. Ed. 2018, 57, 1021.(C₁₀H₂₂N)₂SnBr₄ Morad, V. et al. J. Am. Chem. Soc. 2019, 141, 9764.(C₁₀H₂₂N)₂PbBr₄ Morad, V. et al. J. Am. Chem. Soc. 2019, 141, 9764.(C₁₀H₂₂N)₂GeBr₄ Morad, V. et al. J. Am. Chem. Soc. 2019, 141, 9764.(C₁₃H₁₉N₄)₂PbBr₄ Lin, H. et al. ACS Mater. Lett. 2019, 1, 594.

In some embodiments, the metal halide hybrid includes an organicantimony halide. The organic antimony halide may include a crystalaccording to Formula (I)—

R₂SbX₅  Formula (I),

wherein X is a halide, and R is an organic ammonium cation. The organicammonium cation may include at least one phosphorus atom (e.g., Formula(IIb)).

The organic ammonium cation may have a structure according to Formula(IIa) or Formula (IIb):

wherein each of R¹-R¹⁰ is independently selected from a substituted orunsubstituted C₁-C₂₀ hydrocarbyl.

In some embodiments, the organic ammonium cation is abis(triarylphosphoranylidine) ammonium cation. Thebis(triarylphosphoranylidine) ammonium cation may be abis(triphenyl-phosphoranylidene)ammonium cation.

In some embodiments, the organic ammonium cation is abis(triarylphosphoranylidine) ammonium cation, and X is Cl⁻. Thebis(triarylphosphoranylidine) ammonium cation may be abis(triphenyl-phosphoranylidene)ammonium cation, and X is Cl⁻.

In some embodiments, the metal halide material is a zero-dimensional(0D) organic metal halide hybrid, (PPN)₂SbCl₅(PPN=bis(triphenylphosphoranylidene)ammonium cation), which may be usedas an X-ray scintillation material having a high light yield and/orenvironmental stability. In some embodiments, (PPN)₂SbCl₅ singlecrystals are prepared by solution growth, and exhibit visiblephotoluminescence with a quantum efficiency of 98.1%. In someembodiments, when excited by X-rays, (PPN)₂SbCl₅ single crystals exhibitradioluminescence with a near-perfect linearity in a large range ofX-ray dose rate, and a higher light yield (˜49500 photons per MeV) thanthat of a commercial Lu_(1.8)Y_(0.2)SiO₅:Ce scintillator (˜33200 photonsper MeV). In some embodiments, the detection limit of (PPN)₂SbCl₅ (191.4nGy_(air) s⁻¹) is much lower than the required value for regular medicaldiagnostics (5.5 μGy_(air) s⁻¹). In some embodiments, (PPN)₂SbCl₅ singlecrystals are provided that exhibit significant stability withlittle-to-no change of properties after storage in ambient conditionsfor at least one year, or at least two years.

In some embodiments, the metal halide hybrid is an organic manganese(II) halide hybrid. The organic manganese (II) halide hybrid may includea crystal according to Formula (III)—

R′MnX₄  Formula (III),

wherein X is a halide, and R′ is an organic phosphonium cation. In someembodiments, the crystal exhibits a green emission peaked at 517 nm.

In some embodiments, the organic phosphonium cation has a structureaccording to Formula (IV):

wherein each of R¹¹-R¹⁷ is independently selected from a substituted orunsubstituted C₁-C₂₀ hydrocarbyl.

In some embodiments, the organic phosphonium cation isethylenebis-triphenyl-phosphonium. In some embodiments, the organicphosphonium cation is ethylenebis-triphenyl-phosphonium, and X is Br.

In some embodiments, the metal halide material isethylenebis-triphenylphosphonium manganese (II) bromide((C₃₈H₃₄P₂)MnBr₄). In some embodiments, the materials are prepared usinga facile solution growth method at room temperature to form inch-sizedsingle crystals. In some embodiments, the organic-inorganic hybridmaterials have a zero-dimensional (0D) structure at the molecular level.The materials may exhibit a green emission peaked at 517 nm. Thematerials may have a photoluminescence quantum efficiency (PLQE) ofabout 95%. In some embodiments, the characterization of the materials'X-ray scintillation revealed excellent performance with an exceptionallinear response to X-ray dose rate, a high light yield of about 80,000photons/MeV, and a very low detection limit of 72.8 nGy/s. X-ray imagingtests demonstrated that embodiments of scintillators based on(C₃₈H₃₄P₂)MnBr₄ powders could provide a visualization tool for X-rayradiography, and high resolution flexible scintillators could befabricated by blending (C₃₈H₃₄P₂)MnBr₄ powders with polydimethylsiloxane(PDMS).

Other embodiments of the methods, devices, and metal halide hybridsprovided herein include the following:

Embodiment 1: A method for X-ray scintillation, the method comprisingirradiating a metal halide hybrid with high-energy radiation to convertthe high-energy radiation to at least one of near ultraviolet light orvisible light.

Embodiment 2: The method of Embodiment 1, wherein the metal halidehybrid has a 0D structure.

Embodiment 3: The method of any of the preceding Embodiments, wherein(i) the metal halide hybrid has a first PLQE measured within one week ofthe metal halide hybrid's creation, (ii) a second PLQE measured afterthe metal halide hybrid is stored at ambient conditions for at least oneyear or at least 2 years following the metal halide hybrid's creation,and (iii) the second PLQE is no more than 3 percentage points, 2percentage points, or 1 percentages points less than the first PLQE.

Embodiment 4: The method of any of the preceding Embodiments, whereinthe metal halide hybrid exhibits (i) a light yield of at least 50,000photons/MeV, at least 60,000 photons/MeV, at least 70,000 photons/MeV,or about 70,000 photons/MeV to about 90,000 photons/MeV, (ii) adetection limit of about 50 nGy/s to about 500 nGy/s, or (iii) acombination thereof.

Embodiment 5: The method of any of the preceding Embodiments, whereinthe metal halide hybrid is in the form of one or more discrete crystals.

Embodiment 6: The method of any of the preceding Embodiments, whereineach of the one or more discrete crystals has a largest dimension ofabout 1 mm to about 10 mm.

Embodiment 7: The method of any of the preceding Embodiments, whereinthe metal halide hybrid is dispersed in a matrix material.

Embodiment 8: The method of any of the preceding Embodiments, whereinthe metal halide hybrid is in the form of a powder.

Embodiment 9: The method of any of the preceding Embodiments, whereinthe matrix material comprises a polymer.

Embodiment 10: The method of any of the preceding Embodiments, whereinthe polymer comprises polydimethylsiloxane.

Embodiment 11: The method of any of the preceding Embodiments, whereinthe matrix material is in the form of a film.

Embodiment 12: The method of any of the preceding Embodiments, whereinthe film is a flexible film.

Embodiment 13: The method of any of the preceding Embodiments, whereinthe film comprises a polymeric three-dimensional microstructured film.

Embodiment 14: The method of any of the preceding Embodiments, whereinthe high-energy radiation comprises X-rays, gamma rays, or a combinationthereof.

Embodiment 15: The method of any of the preceding Embodiments, whereinthe high-energy radiation comprises X-rays, and the metal halide hybridis irradiated with the X-rays at a dose rate of about 5 microGy/s toabout 100 microGy/s, about 5 microGy/s to about 80 microGy/s, about 10microGy/s to about 60 microGy/s, or about 10 microGy/s to about 40microGy/s.

Embodiment 16: A device comprising an electronic substrate; an imagingchip; a fiber-optic face plate, wherein the imaging chip is arrangedbetween the electronic substrate and the fiber-optic face plate; and ascintillator screen comprising a metal halide hybrid, wherein thefiber-optic face plate is arranged between the imaging chip and thescintillator screen.

Embodiment 17: The device of any of the preceding Embodiments, whereinthe metal halide hybrid has a 0D structure.

Embodiment 18: The device of any of the preceding Embodiments, furthercomprising a housing in which the electronic substrate, the imagingchip, the fiber-optic face plate, and the scintillator screen arearranged.

Embodiment 19: The device of any of the preceding Embodiments, whereinthe imaging chip comprises a complementary metal oxide semiconductorimage sensor.

Embodiment 20: The device of any of the preceding Embodiments, whereinthe metal halide hybrid is in the form of one or more discrete crystalsdispersed in the scintillator screen, arranged on the scintillatorscreen, or a combination thereof.

Embodiment 21: The device of any of the preceding Embodiments, whereinthe scintillator screen further comprises a matrix material in which themetal halide hybrid is dispersed.

Embodiment 22: The device of any of the preceding Embodiments, whereinthe scintillator screen is a flexible film.

Embodiment 23: The method or device of any of the preceding Embodiments,wherein the metal halide hybrid comprises an organic metal halidehybrid.

Embodiment 24: The method or device of any of the preceding Embodiments,wherein the organic metal halide hybrid comprises an organic metal mixedhalide hybrid.

Embodiment 25: The method or device of any of the preceding Embodiments,wherein the metal halide hybrid comprises an inorganic metal halidehybrid.

Embodiment 26: The method or device of any of the preceding Embodiments,wherein the inorganic metal halide hybrid comprises an inorganic metalmixed halide hybrid.

Embodiment 27: The method or device of any of the preceding Embodiments,wherein the metal halide hybrid comprises an organic-inorganic metalhalide hybrid.

Embodiment 28: The method or device of any of the preceding Embodiments,wherein the organic-inorganic metal halide hybrid comprises anorganic-inorganic metal mixed halide hybrid.

Embodiment 29: The method or device of any of the preceding Embodiments,wherein the metal halide hybrid comprises a metal selected from thegroup consisting of Sn, In, Sb, Bi, Mn, Hg, Zn, and Ge.

Embodiment 30: The method or device of any of the preceding Embodiments,wherein the halide comprises F⁻, Cl⁻, Br⁻, I⁻, or a combination thereof.

Embodiment 31: The method or device of any of the preceding Embodiments,wherein the metal halide hybrid comprises an inorganic cation comprisingcesium.

Embodiment 32: The method or device of any of the preceding Embodiments,wherein the metal halide hybrid comprises an organic cation selectedfrom the group consisting of an ammonium cation and a phosphoniumcation.

Embodiment 33: The method or device of any of the preceding Embodiments,wherein the metal halide hybrid comprises an organic antimony halidecomprising a crystal according to Formula (I)—R₂SbX₅ Formula (I),wherein X is a halide, and wherein R is an organic ammonium cation.

Embodiment 34: The method or device of any of the preceding Embodiments,wherein the metal halide hybrid comprises an organic manganese (II)halide hybrid comprising a crystal according to Formula (III)—R′MnX₄Formula (III), wherein X is a halide, and R′ is an organic phosphoniumcation.

Embodiment 35: An organic antimony halide comprising a crystal accordingto Formula (I)—R₂SbX₅ Formula (I), wherein X is a halide, and wherein Ris an organic ammonium cation.

Embodiment 36: The organic antimony halide of any of the precedingEmbodiments, wherein the organic ammonium cation has a structureaccording to formula (IIa) or formula (IIb):

wherein each of R¹-R¹⁰ is independently selected from a substituted orunsubstituted C₁-C₂₀ hydrocarbyl.

Embodiment 37: The organic antimony halide of any of the precedingEmbodiments, wherein the organic ammonium cation comprises at least onephosphorus atom.

Embodiment 38: The organic antimony halide of any of the precedingEmbodiments, wherein the organic ammonium cation is abis(triarylphosphoranylidine)ammonium cation.

Embodiment 39: The organic antimony halide of any of the precedingEmbodiments, wherein the bis(triarylphosphoranylidine) ammonium cationis bis(triphenylphosphoranylidene) ammonium cation.

Embodiment 40: The organic antimony halide of any of the precedingEmbodiments, wherein X is Cl.

Embodiment 41: The organic antimony halide of any of the precedingEmbodiments, wherein the crystal has a 0D structure.

Embodiment 42: The organic antimony halide of any of the precedingEmbodiments, wherein the crystal comprises a single crystal having alargest dimension of about 1 mm to about 10 mm.

Embodiment 43: The organic antimony halide of any of the precedingEmbodiments, wherein the crystal has a PLQE of at least 97%.

Embodiment 44: The organic antimony halide of any of the precedingEmbodiments, wherein the crystal has a PLQE of at least 98%.

Embodiment 45: The organic antimony halide of any of the precedingEmbodiments, wherein (i) the crystal has a first PLQE measured withinone week of the crystal's creation, (ii) a second PLQE measured afterthe crystal is stored at ambient conditions for at least one year or atleast 2 years following the crystal's creation, and (iii) the secondPLQE is no more than 3 percentage points, 2 percentage points, or 1percentage point less than the first PLQE.

Embodiment 46: A scintillator screen comprising the organic antimonyhalide of any one of the previous Embodiments.

Embodiment 47: A method or device of any one of Embodiments 1 to 34,wherein the metal halide hybrid comprises the organic antimony halidehybrid of any one of

Embodiments 35 to 45.

Embodiment 48: An organic manganese (II) halide hybrid comprising acrystal according to Formula (III)—R′MnX₄ Formula (III), wherein X is ahalide, and R′ is an organic phosphonium cation.

Embodiment 49: The organic manganese (II) halide hybrid of any of thepreceding Embodiments, wherein the organic phosphonium cation has astructure according to Formula (IV):

wherein each of R¹¹-R¹⁷ is independently selected from a substituted orunsubstituted C₁-C₂₀ hydrocarbyl.

Embodiment 50: The organic manganese (II) halide hybrid of any of thepreceding Embodiments, wherein the organic phosphonium cation isethylenebis-triphenylphosphonium.

Embodiment 51: The organic manganese (II) halide hybrid of any of thepreceding Embodiments, wherein X is Br.

Embodiment 52: The organic manganese (II) halide hybrid of any of thepreceding Embodiments, wherein the crystal has a 0D structure.

Embodiment 53: The organic manganese (II) halide hybrid of any of thepreceding Embodiments, wherein the crystal exhibits a green emissionpeaked at 517 nm.

Embodiment 54: The organic manganese (II) halide hybrid of any of thepreceding Embodiments, wherein the crystal has a PLQE of at least 95%.

Embodiment 55: The organic manganese (II) halide hybrid of any of thepreceding Embodiments, wherein the crystal exhibits a (i) light yield ofat least 50,000 photons/MeV, at least 60,000 photons/MeV, at least70,000 photons/MeV, or about 70,000 to about 90,000 photons/MeV, (ii) adetection limit of about 50 nGy/s to about 100 nGy/s, or (iii) acombination thereof.

Embodiment 56: A scintillator screen comprising the organic manganese(II) halide hybrid of any one of Embodiments 48 to 55.

Embodiment 57: A method or device of any one of Embodiments 1 to 34,wherein the metal halide hybrid comprises the organic manganese (II)halide hybrid of any one of

Embodiments 48 to 55.

The phrases “C₁-C₂₀ hydrocarbyl,” and the like, as used herein,generally refer to aliphatic, aryl, or arylalkyl groups containing 1 to20 carbon atoms. Examples of aliphatic groups, in each instance,include, but are not limited to, an alkyl group, a cycloalkyl group, analkenyl group, a cycloalkenyl group, an alkynyl group, an alkadienylgroup, a cyclic group, and the like, and includes all substituted,unsubstituted, branched, and linear analogs or derivatives thereof, ineach instance having 1 to about 20 carbon atoms. Examples of alkylgroups include, but are not limited to, methyl, ethyl, propyl,isopropyl, n-butyl, t-butyl, isobutyl, pentyl, hexyl, isohexyl, heptyl,4,4-dimethylpentyl, octyl, 2,2,4-trimethylpentyl, nonyl, decyl, undecyland dodecyl. Cycloalkyl moieties may be monocyclic or multicyclic, andexamples include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, andadamantyl. Additional examples of alkyl moieties have linear, branchedand/or cyclic portions (e.g., 1-ethyl-4-methyl-cyclohexyl).Representative alkenyl moieties include vinyl, allyl, 1-butenyl,2-butenyl, isobutylenyl, 1-pentenyl, 2-pentenyl, 3-methyl-1-butenyl,2-methyl-2-butenyl, 2,3-dimethyl-2-butenyl, 1-hexenyl, 2-hexenyl,3-hexenyl, 1-heptenyl, 2-heptenyl, 3-heptenyl, 1-octenyl, 2-octenyl,3-octenyl, 1-nonenyl, 2-nonenyl, 3-nonenyl, 1-decenyl, 2-decenyl and3-decenyl. Representative alkynyl moieties include acetylenyl, propynyl,1-butynyl, 2-butynyl, 1-pentynyl, 2-pentynyl, 3-methyl-1-butynyl,4-pentynyl, 1-hexynyl, 2-hexynyl, 5-hexynyl, 1-heptynyl, 2-heptynyl,6-heptynyl, 1-octynyl, 2-octynyl, 7-octynyl, 1-nonynyl, 2-nonynyl,8-nonynyl, 1-decynyl, 2-decynyl and 9-decynyl. Examples of aryl orarylalkyl moieties include, but are not limited to, anthracenyl,azulenyl, biphenyl, fluorenyl, indan, indenyl, naphthyl, phenanthrenyl,phenyl, 1,2,3,4-tetrahydro-naphthalene, tolyl, xylyl, mesityl, benzyl,and the like, including any heteroatom substituted derivative thereof.

Unless otherwise indicated, the term “substituted,” when used todescribe a chemical structure or moiety, refers to a derivative of thatstructure or moiety wherein one or more of its hydrogen atoms issubstituted with a chemical moiety or functional group such as alcohol,alkoxy, alkanoyloxy, alkoxycarbonyl, alkenyl, alkyl (e.g., methyl,ethyl, propyl, t-butyl), alkynyl, alkylcarbonyloxy (—OC(O)alkyl), amide(—C(O)NH-alkyl- or -alkylNHC(O)alkyl), tertiary amine (such asalkylamino, arylamino, arylalkylamino), aryl, aryloxy, azo, carbamoyl(—NHC(O)O-alkyl- or —OC(O)NH-alkyl), carbamyl (e.g., CONH₂, as well asCONH-alkyl, CONH-aryl, and CONH-arylalkyl), carboxyl, carboxylic acid,cyano, ester, ether (e.g., methoxy, ethoxy), halo, haloalkyl (e.g.,—CCl₃, —CF₃, —C(CF₃)₃), heteroalkyl, isocyanate, isothiocyanate,nitrile, nitro, phosphodiester, sulfide, sulfonamido (e.g., SO₂NH₂),sulfone, sulfonyl (including alkylsulfonyl, arylsulfonyl andarylalkylsulfonyl), sulfoxide, thiol (e.g., sulfhydryl, thioether) orurea (—NHCONH-alkyl-).

All referenced publications are incorporated herein by reference.Furthermore, where a definition or use of a term in a reference, whichis incorporated by reference herein, is inconsistent or contrary to thedefinition of that term provided herein, the definition of that termprovided herein applies and the definition of that term in the referencedoes not apply.

While certain aspects of conventional technologies have been discussedto facilitate disclosure of various embodiments, applicants in no waydisclaim these technical aspects, and it is contemplated that thepresent disclosure may encompass one or more of the conventionaltechnical aspects discussed herein.

The present disclosure may address one or more of the problems anddeficiencies of known methods and processes. However, it is contemplatedthat various embodiments may prove useful in addressing other problemsand deficiencies in a number of technical areas. Therefore, the presentdisclosure should not necessarily be construed as limited to addressingany of the particular problems or deficiencies discussed herein.

In this specification, where a document, act or item of knowledge isreferred to or discussed, this reference or discussion is not anadmission that the document, act or item of knowledge or any combinationthereof was at the priority date, publicly available, known to thepublic, part of common general knowledge, or otherwise constitutes priorart under the applicable statutory provisions; or is known to berelevant to an attempt to solve any problem with which thisspecification is concerned.

In the descriptions provided herein, the terms “includes,” “is,”“containing,” “having,” and “comprises” are used in an open-endedfashion, and thus should be interpreted to mean “including, but notlimited to.” When methods or apparatuses are claimed or described interms of “comprising” various steps or components, the methods orapparatuses can also “consist essentially of” or “consist of” thevarious steps or components, unless stated otherwise.

The terms “a,” “an,” and “the” are intended to include pluralalternatives, e.g., at least one. For instance, the disclosure of “acrystal,” “a halide,” “a scintillation material”, and the like, is meantto encompass one, or mixtures or combinations of more than one crystal,halide, scintillation material, and the like, unless otherwisespecified.

Various numerical ranges may be disclosed herein. When Applicantdiscloses or claims a range of any type, Applicant's intent is todisclose or claim individually each possible number that such a rangecould reasonably encompass, including end points of the range as well asany sub-ranges and combinations of sub-ranges encompassed therein,unless otherwise specified. Moreover, all numerical end points of rangesdisclosed herein are approximate. As a representative example, Applicantdiscloses, in some embodiments, that a crystal comprises a singlecrystal having a largest dimension of about 1 mm to about 10 mm. Thisrange should be interpreted as encompassing about 1 mm to about 10 mm,and further encompasses “about” each of 2 mm, 3 mm, 4 mm, 5 mm, 6 mm, 7mm, 8 mm, and 9 mm, including any ranges and sub-ranges between any ofthese values.

As used herein, the term “about” means plus or minus 10% of thenumerical value of the number with which it is being used.

EXAMPLES

The present invention is further illustrated by the following examples,which are not to be construed in any way as imposing limitations uponthe scope thereof. On the contrary, it is to be clearly understood thatresort may be had to various other aspects, embodiments, modifications,and equivalents thereof which, after reading the description herein, maysuggest themselves to one of ordinary skill in the art without departingfrom the spirit of the present invention or the scope of the appendedclaims. Thus, other aspects of this invention will be apparent to thoseskilled in the art from consideration of the specification and practiceof the invention disclosed herein.

Example 1—Highly Efficient Eco Friendly X-Ray Scintillators Based on anOrganic Manganese Halide

In this example, a new 0D organic manganese (II) halide hybrid(C₃₈H₃₄P₂)MnBr₄ was synthesized, which exhibited highly efficient greenemission upon photo and X-ray excitations. Single crystals with sizesof >1 cm were prepared via a facile solution growth method at roomtemperature, which showed remarkable scintillation properties withexcellent response linearity to dose rate, high light yield, and lowdetection limits. X-ray imaging was successfully demonstrated with highresolution. The low-cost, facile preparation, environmentally friendly,and state-of-the-art scintillation performance made this organicmanganese (II) hybrid (C₃₈H₃₄P₂)MnBr₄ a highly promising scintillatorfor commercial applications.

The following materials were used in this example. Manganese (II)bromide, and Ethylenebis(triphenylphosphonium bromide) were purchasedfrom Sigma-Aldrich. Dimethylformamide (DMF, 99.8%), Dichloromethane(DCM, 99.9%), Diethyl ether (Et₂O, 99.8%) was purchased from VWR.Standard scintillator Ce:LuAG was purchased from Jiaxing AOSITEPhotonics Technology Co., Ltd. All reagents and solvents were usedwithout further purification unless otherwise stated.

Growth of 0D (C₃₈H₃₄P₂)MnBr₄ Single crystals. MnBr₂ (1.0 mmol) andEthylenebis(triphenylphosphonium bromide) (1.0 mmol) were dissolved in 2mL DCM solution and then filtered into a small vial to form a clearprecursor solution. The small vial was then put in a larger vial with 10mL of Et₂O inside. The as-prepared solution was sealed and left to standfor about 3 days to afford pale green block crystals. The crystals wereobtained at a yield of about 89%.

Scintillator screen. Firstly, (C₃₈H₃₄P₂)MnBr₄ single crystals werehand-ground to fine powders by using mortar and pestle. Then thescintillator screen was prepared by filling the fine powder into thePXRD holder. The flexible screen was prepared by blending the powderwith a two-part polydimethylsiloxane (PDMS) EI-1184 at a concentrationof 800 mg/ml. The mixture gel was placed in a polytetrafluoroethylene(PTFE) mold and cured at 100° C. for 30 minutes, under ambientatmosphere.

Single crystal X-ray diffraction (SCXRD). Single crystal X-ray data forthe (C₃₈H₃₄P₂)MnBr₄ hybrid were collected using a Rigaku XtaLABSynergy-S diffractometer equipped with a HyPix-6000HE Hybrid PhotonCounting (HPC) detector and dual Mo and Cu microfocus sealed X-raysource.

Powder X-ray diffraction (PXRD). The PXRD analysis was performed onPanalytical X'PERT Pro Powder X-Ray Diffractometer using Copper X-raytube (standard) radiation at a voltage of 40 kV and 40 mA, andX'Celerator RTMS detector. The diffraction pattern, S, was scanned overthe angular range of 5-40 degree (20) with a step size of 0.02, at roomtemperature.

Absorption spectrum measurements. Absorption spectra of (C₃₈H₃₄P₂)MnBr₄hybrid were measured at room temperature on Cary 5000 UV-Vis-NIRspectrophotometer.

Photoluminescence steady state studies. Steady-state photoluminescencespectrum of (C₃₈H₃₄P₂)MnBr₄ was obtained at room temperature on a FS5spectrofluorometer (Edinburgh Instruments).

Photoluminescence quantum efficiency (PLQE). The PLQEs were acquiredusing a Hamamatsu Quantaurus-QY Spectrometer (Model C11347-11) equippedwith a xenon lamp, integrated sphere sample chamber and CCD detector.The PLQEs were calculated by the equation: ηQE=IS/(ER−ES), in which ISrepresents the luminescence emission spectrum of the sample, ER is thespectrum of the excitation light from the empty integrated sphere(without the sample), and ES is the excitation spectrum for exciting thesample.

Time-resolved photoluminescence. Time-Resolved Emission data werecollected at room temperature using the Edinburgh FLS920 fluorescencespectrometer. The dynamics of emission decay were monitored by using thetime-correlated single-photon counting capability with data collectionfor 10,000 counts. The average lifetime was obtained bysingle-exponential fitting.

Thermogravimetric analysis (TGA). TGA was carried out using a TAinstruments Q50 TGA system. The samples were heated from roomtemperature (around 25° C.) to 700° C. at a rate of 5° C. min⁻¹, under anitrogen flux of 100 ml min⁻¹.

Radioluminescence (RL) and X-ray imaging. The spectra ofradioluminescence was acquired by using an Edinburgh FS5spectrofluorometer (Edinburgh Instruments) equipped with a X-ray source(Amptek Mini-X tube with a Au target and 4 W maximum power output). Theradiation dose rate of the X-ray source was calibrated by using an ionchamber dosimeter. The X-ray images are acquired by using digital camera(Nikon D90).

Scanning electron microscopy (SEM). The particle size of (C₃₈H₃₄P₂)MnBr₄fine powders were investigated by FEI Nova NanoSEM 400 scanning electronmicroscope.

In this example, high performance eco-friendly X-ray scintillators basedon a 0D phosphonium manganese (II) bromide hybrid (C₃₈H₃₄P₂)MnBr₄ wereprepared.

The organic manganese (II) halide hybrid of this example was easilyprepared by using low-cost commercially available raw materials via afacile room temperature solvent diffusion method with excellentrepeatability and large scalability. High quality (C₃₈H₃₄P₂)MnBr₄ singlecrystals of this example with sizes of >1 cm showed great thermalstability and bright green emission peaked at 517 nm with a PLQE of˜95%. Scintillators based on (C₃₈H₃₄P₂)MnBr₄ displayed great performancewith exceptional linearity, high light yield, and low detection limits,which enabled high resolution X-ray images.

In this example, 0D (C₃₈H₃₄P₂)MnBr₄ single crystals were obtained bydiffusing diethyl ether into a dichloromethane (DCM) precursor solutioncontaining ethylenebis(triphenyl-phosphonium bromide) (C₃₈H₃₄P₂Br₂) andMnBr₂ in a ratio of 1:1.

The crystal structure of (C₃₈H₃₄P₂)MnBr₄ single crystals was determinedby single crystal X-ray diffraction (SCXRD). (C₃₈H₃₄P₂)MnBr₄crystallized at a monoclinic space group of C_(2/c), and possessed a 0Dstructure at the molecular level with MnBr₄ tetrahedrons isolated andsurrounded by C₃₈H₃₄P₂ ²⁺ cations. The manganese center adopted atypical tetra-coordinated geometry bonded to bromide ions, with anaverage Mn—Br bond length of 2.51 Å and bond angle of 108.48 (seedetails in Table A and Table B), similar to those of previously reportedMnBr₄ complexes (Xu, L. J., Sun, C. Z., Xiao, H., Wu, Y., Chen, Z. N.Green-Light-Emitting Diodes based on Tetrabromide Manganese(II) Complexthrough Solution Process. Advanced Materials 2017, 29(10)).

TABLE A Single X-ray diffraction data of (C₃₈H₃₄P₂)MnBr₄ Compound(C₃₈H₃₄P₂)MnBr₄ Empirical formula C₃₈H₃₄Br₄P₂Mn Molecular weight 927.13Temperature/K 293(2) Crystal system monoclinic Space group C_(2/c) a/Å10.108(3) b/Å 18.594(5) c/Å 20.176(6) α/° 90 β/° 99.860(4) γ/° 90Volume/Å³ 3736.0(19) Z 4 ρ_(calc)g/cm³ 1.648 μ/mm⁻¹ 4.743 R₁, wR₂0.0305^(a), 0.1110^(b) Goodness-of-fit on F² 0.835 $\begin{matrix}{{^{a)}R1} = {\Sigma{❘{{❘F_{o}❘} - {❘{F_{c}{❘{{❘{/\Sigma}❘}F_{o}{❘{❘.}}}}}}}}}} \\{{^{b)}{wR}2} = \left\lbrack {\Sigma{{w\left( {F_{o}^{2} - F_{c}^{2}} \right)}^{2}/\Sigma}{w\left( F_{o}^{2} \right)}^{2}} \right\rbrack^{1/2}}\end{matrix}$

TABLE B Selected bond length and bond angle of (C₃₈H₃₄P₂)MnBr₄ BondDistance (Å) Mn1—Br1 2.505 Mn1—Br2 2.520 Bonds Angle (°) Br1—Mn1—Br1A101.6 Br1—Mn1—Br2 113.5 Br1—Mn1—Br2A 106.8 Br2—Mn1—Br2A 114.0

The powder X-ray diffraction pattern of (C₃₈H₃₄P₂)MnBr₄ powders wasidentical to the simulated result from SCXRD data, which suggested thehigh phase purity of the as-prepared single crystals. No weight loss wasobserved before 310° C. in thermogravimetric analysis (TGA), whichsuggested a high thermal stability.

The (C₃₈H₃₄P₂)MnBr₄ single crystals were pale green under ambient lightand became highly emissive upon irradiating with UV light as shown atFIG. 2 .

The photophysical properties were further investigated using UV-visabsorption and steady-state photoluminescence (PL) spectroscopies. Asshown in FIG. 2 , (C₃₈H₃₄P₂)MnBr₄ exhibited an intense absorption bandaround 285 nm along with two absorption peaks at 360 and 450 nm. Theexcitation spectra had the same features as absorption spectra inlow-energy band, which corresponded to two groups of transitions: ⁶A₁→⁴Gand ⁶A₁→⁴D. Upon irradiation in the range of 300-400 nm, bright greenemission peaked at 517 nm was observed with a full width at half maximum(FWHM) of 51 nm, a high PLQE of ˜95% and a long lifetime of 318 μs. Thestrong green emission was well known to be from d-d⁴T₁→⁶A₁ transition ofMn²⁺ ion with a tetrahedral coordination geometry. Moreover,(C₃₈H₃₄P₂)MnBr₄ demonstrated great moisture stability with PL intensityunchanged after exposure in ambient atmosphere for one month, asdepicted at FIG. 3 . The high emission efficiency together with goodquality of easily prepared single crystals suggested the suitability of(C₃₈H₃₄P₂)MnBr₄ for luminescent devices.

To explore the scintillation performance of (C₃₈H₃₄P₂)MnBr₄, acommercially available scintillation material, cerium-doped lutetiumaluminum garnet (Ce:LuAG), was used as a standard reference as itexhibits a similar PL emission peaked at around 520 nm. The X-rayradioluminescence (RL) spectra of (C₃₈H₃₄P₂)MnBr₄ and Ce:LuAG wereobtained by using Edinburgh FS5 fluorescence spectrophotometer equippedwith a X-ray generator (Amptek Mini-X tube, Au target, 4 W). As shown atFIG. 4A and FIG. 4B, both RL emissions were identical to their PLemissions. Interestingly, the RL intensity of (C₃₈H₃₄P₂)MnBr₄ was morethan 3 times higher than that of Ce:LuAG under the same X-ray dose rateirradiation.

Moreover, the X-ray image of (C₃₈H₃₄P₂)MnBr₄ single crystals was muchbrighter than that of Ce:LuAG (specifically, (C₃₈H₃₄P₂)MnBr₄ singlecrystals exhibited an RL intensity of about 16 10¹⁰ cps at an X-ray doserate of 20.8 microGy/s, while, under the same conditions, Ce:LuAGexhibited an RL intensity of about 4.2 10¹⁰ cps), which suggested that(C₃₈H₃₄P₂)MnBr₄ was more sensitive to X-ray irradiation than Ce:LuAG. Toevaluate the scintillator response to X-ray dose rate, the RLintensities were measured under various X-ray dose rates for(C₃₈H₃₄P₂)MnBr₄ and Ce:LuAG. Both scintillators exhibited excellentlinearities to the X-ray dose rates in a large range from 36.7 nGy/s to89.4 μGy/s. Moreover, (C₃₈H₃₄P₂)MnBr₄ exhibited a higher response toX-ray dose than Ce:LuAG with a larger slope. The detection limits ofX-ray dose rate was measured to be 72.8 nGy/s for (C₃₈H₃₄P₂)MnBr₄, whichis about 75 times lower than the dose rate required for X-raydiagnostics (5.5 μGy/s). Light yield was another important parameter toevaluate the performance of scintillators, which was dependent on theamplitude of X-ray response and the RL spectra. Since the X-ray doseresponse of (C₃₈H₃₄P₂)MnBr₄ was 3.2 times higher than that of Ce:LuAG(with a light yield of 25,000 Ph/MeV) and they had a similar RL spectra,the light yield of (C₃₈H₃₄P₂)MnBr₄ could be derived to be around 79,800Photon/MeV.

As shown at FIG. 5A, the light yield of (C₃₈H₃₄P₂)MnBr₄ was much betterthan those of widely investigated CsPbBr₃ nanocrystals and manycommercially available scintillators, such as CsI(TI), YAG(Ce) andLuBr₃(Ce). The stability of (C₃₈H₃₄P₂)MnBr₄ single crystals againstX-ray irradiation was evaluated by monitoring the changes of RLintensity under continuous X-ray irradiation with a dose rate of 26μGy/s. FIG. 5B shows that no radio-degradation was observed after 2 hexposure to X-ray irradiation, suggesting high stability forscintillator application.

To further validate the potential of (C₃₈H₃₄P₂)MnBr₄ as scintillationmaterial for practical X-ray imaging, a home-built X-ray imaging systemwas constructed. The scintillator screen was prepared by refilling aglass holder with (C₃₈H₃₄P₂)MnBr₄ fine powders with the particle sizeless than 3 μm (SEM images of the powders were collected). A speakerchip with a size of 9 mm×6 mm was used as target placed between theX-ray source and the scintillator screen for X-ray image. Theconfiguration inside of the chip could not be seen directly with thenaked eye, but was revealed clearly with X-ray imaging using a(C₃₈H₃₄P₂)MnBr₄ based scintillator. The large difference in X-rayabsorption for different materials in the chip resulted in spatialintensity contrast displayed in the scintillator screen. The excellentperformance of X-ray imaging could be attributed to the high PLQE, lightyield, and/or low detection limit of (C₃₈H₃₄P₂)MnBr₄.

In this example, flexible scintillators with large size (4.5×5.8 cm)were demonstrated by blending (C₃₈H₃₄P₂)MnBr₄ fine powders with PDMS.The resulting films showed excellent flexibility, which could be easilybended and stretched. Moreover, the film showed high uniformity andstrong emission under UV irradiation. To demonstrate the capability ofthe X-ray imaging, a wrench and speaker chip were scanned as thetargets. Distinct color contrast and detail inside of the chip could bedisplayed in the flexible film with good resolution.

Example 2—Highly Stable Lead-Free Organic Antimony Halide Crystals forX-Ray Scintillation

In this example, the following materials were used: Antimony (III)chloride (SbCl₃, 99.95%), bis(triphenylphosphoranylidene)ammoniumchloride (PPNCl, 97%), and Dichloromethane (DCM, ≥99.8%) were purchasedfrom Sigma-Aldrich. Dimethylformamide (DMF, 99.8%) and diethyl ether(Et₂O, anhydrous) were bought for VWR.

In this example, (PPN)₂SbCl₅ single crystals were prepared by injectingdiethyl ether into a dichloromethane precursor solution of SbCl₃ andPPNCl at room temperature in an N₂-filled glovebox and stood forovernight. The detailed synthesis and characterization are describedbelow.

The crystal structure of the obtained (PPN)₂SbCl₅ single crystals wasdetermined by single crystal X-ray diffraction (SCXRD) at 150 K. Theresults indicated that the isolated SbCl₅ anions ionically bonded tosurrounding bulky PPN⁺ cations, forming a typical 0D organic-inorganicmetal halide hybrid structure with monoclinic P2_(1/c) symmetry (TableC).

TABLE C Single crystal XRD data and the corresponding collectionparameters of (PPN)₂SbCl₅. The data was recorded at a temperature of 150K. Compound Antimony pentachloridebis(triphenylphosphoranylidene)ammonium Empirical C₇₂H₆₀N₂P₄SbCl₅formula Formula weight 1376.10 Temperature/K 149.99(10) Crystal systemmonoclinic Space group P2₁/c a/Å 11.0421(2) b/Å 24.1416(4) c/Å24.0743(4) α/° 90 β/° 90.6060(10) γ/° 90 Volume/Å³ 6417.22(19) Z 4ρ_(calc)g/cm³ 1.424 μ/mm⁻¹ 0.783 Crystal size/mm³ 0.303 × 0.264 × 0.128Radiation Mo Kα (λ = 0.71073) 2Θ range for 3.688 to 65.202 datacollection/° Index ranges −15 ≤ h ≤ 14, −34 ≤ k ≤ 32, −32 ≤ l ≤ 36Reflections 92625 collected Independent 19486 [R_(int) = 0.0524,R_(sigma) = 0.0424] reflections Data/restraints/ 19486/0/757 parametersGoodness-of-fit 1.086 on F² Final R indexes R₁ = 0.0346, wR₂ = 0.0840[I >= 2σ (I)] Final R indexes R₁ = 0.0470, wR₂ = 0.0881 [all data]Largest diff. 0.60/−0.68 peak/hole/e Å⁻³

TABLE D Selected bond lengths and bond angles of (PPN)₂SbCl₅. Atom AtomLength/Å Atom Atom Atom Angle/° Sb1 Cl1 2.3810(4) Cl1 Sb1 Cl2 87.908(19) Sb1 Cl2 2.6397(5) Cl1 Sb1 Cl3  89.713(16) Sb1 Cl3 2.5964(5)Cl1 Sb1 Cl4  87.314(16) Sb1 Cl4 2.5876(4) Cl1 Sb1 Cl5  88.669(15) Sb1Cl5 2.6363(5) Cl3 Sb1 Cl2  91.274(19) Cl3 Sb1 Cl5 177.896(15) Cl4 Sb1Cl2 175.209(19) Cl4 Sb1 Cl3  89.059(15)

A single SbCl₅ ⁻ anion showed that each antimony atom was bonded to fivechlorine atoms to form the pyramid structure. The bond distance betweenSb atom and apical Cl atom in SbCl₅ ²⁻ anion was ˜2.38 Å, while thelengths of the other Sb—Cl bonds were from 2.58 to 2.64 Å, which werecomparable to reported SbCl₅ ²⁻ structures (Table D). The powder XRDpattern of ground (PPN)₂SbCl₅ crystals was consistent with the simulatedresult based on its single crystal structure, confirming the reliabilityof SCXRD measurement. This result also suggested the uniformity of 0Dcrystals and the structure stability of single crystals at lowtemperature (150 K).

(PPN)₂SbCl₅ single crystals with a size of several millimeters werelight-yellow under ambient light, and the corresponding band gap wascalculated to be ˜2.7 eV from UV-Vis spectrum. Under UV lightirradiation (365 nm), the crystals displayed bright salmon pinkluminescence with a high photoluminescence quantum efficiency (PLQE) of98.1%.

The photophysical properties of (PPN)₂SbCl₅ crystals were furtherinvestigated with steady photoluminescence (PL) and time-resolvedphotoluminescence (TRPL) spectra (FIG. 6A and FIG. 6B). PL spectrarevealed that single crystals excited at 410 nm had a low-energy (LE)emission peaked at 635 nm with a large full width at half-maximum (FWHM)of 142 nm and a large Stokes shift of 225 nm (FIG. 6A), and a long decaylifetime (τ_(LE)) of 4.1 μs (FIG. 6B). This emission likely stemmed fromthe inorganic SbCl₅ ²⁻ pyramids, as a result of excited state structuralreorganization.

A new high-energy (HE) emission peak located at 480 nm was observed whenthe single crystals were excited at 310 nm (FIG. 6B), which had a decaylifetime (τ_(HE)) of 5.4 ns (FIG. 6C), which suggested that anotheremitting center that could possibly be the organic component. To revealthe origin of this HE emission, PPNCl single crystals were prepared andmeasured to explore the luminescence of the organic component. Theemission peaks of PPNCl appeared at around 480 nm, which was similarwith the HE emission peak of (PPN)₂SbCl₅, which indicated that theorganic component was likely responsible for HE emission.

Meanwhile, the fluorescence emission likely stemmed from singlet STEs ofSbCl₅ ²⁻ pyramids previously observed in this region (see Li, Z. et al.,Dual-Band Luminescent Lead-Free Antimony Chloride Halides withNear-Unity Photoluminescence Quantum Efficiency. Chem. Mater. 2019, 31,9363-9371), which might also have attributed to the HE emission of(PPN)₂SbCl₅. Therefore, the HE emitting center could be assigned tointra-ligand charge transfer (ILCT) of organic cations PPN⁺ and singletself-trapped excitons (STEs) of SbCl₅ ²⁻. Moreover, the PL spectra wasalso measured for (PPN)₂SbCl₅ crystals with excitation wavelengthsvarying from 280 to 380 nm, and it was found that the intensity ofhigh-energy emission peak enhanced firstly and then disappeared (FIG. 7), resulting in excitation-dependent emission profiles.

Considering the high PLQE, the obtained 0D (PPN)₂SbCl₅ single crystalscould be a candidate as a scintillation material for X-ray radiationdetection. Here, an RL spectrum of (PPN)₂SbCl₅ was measured under 50 KeVX-ray excitation to investigate its scintillation performance (FIG. 8A).A commercially available cerium doped lutetium-based scintillator (LYSO)was used as a reference to quantify the scintillation light yield of(PPN)₂SbCl₅. Under X-ray irradiation, (PPN)₂SbCl₅ single crystalsexhibited similar spectrum with dual-band emission at ˜480 and 635 nm asthat of samples excited at 360 nm UV light, while LYSO also exhibitedthe same phenomenon, which indicated the same radiative recombinationchannel under X-ray and UV excitations. Importantly, a high channelnumber of (PPN)₂SbCl₅ (5.73×10¹¹ cps) at the full energy peak wasrecorded, which suggested a higher light yield than that of LYSO(3.86×10¹¹ cps).

To further evaluate the scintillation performance, RL spectra of(PPN)₂SbCl₅ and LYSO crystals under varied X-ray dose rates weremeasured by changing the powder of X-ray tube. The RL intensities ofboth (PPN)₂SbCl₅ and LYSO were enhanced with the increasing of X-raydose rate. Moreover, a linear relationship of X-ray dose rate versus RLintensity was recorded for (PPN)₂SbCl₅ in a large range from ˜10 nGy_(air) s⁻¹ to 90 μGy_(air) s⁻¹ (FIG. 8B). The slope value of(PPN)₂SbCl₅ was ˜1.5 times higher than that of LYSO.

Thus, the light yield of (PPN)₂SbCl₅ could be estimated to be ˜49500 phMeV⁻¹, by referring to LYSO (33200 ph MeV⁻¹). The response of(PPN)₂SbCl₅ also displayed a well linearity at the low range of X-raydose rate (FIG. 8C), with a low detection limit of 191.4 nGy_(air) s⁻¹,which was much lower than that of LYSO (3.5 μGy_(air) s⁻¹) and therequirement for regular medical diagnostics (5.5 μGy_(air) s⁻¹). Bycomparing with some other commercially available scintillators (FIG.8D), it was found that the X-ray irradiation yield of (PPN)₂SbCl₅ washigher than or comparable with existing scintillators, indicating adesirable property for scintillation applications. The remarkablescintillation performance of (PPN)₂SbCl₅ could be attributed to itsnear-unity PLQE and large Stokes shift which resulted in high lightyield and less self-absorption of luminescence, respectively.

The stability of (PPN)₂SbCl₅ was characterized in various aspects. Asshown at FIG. 8E, (PPN)₂SbCl₅ had almost no light yield degradation uponcontinuous X-ray irradiation (90 μGy_(air) s⁻¹) for two hours. Underhigh-intensity UV illumination generated by a high-power mercury lamp(150 mW cm⁻²) for two hours, the PL intensity of (PPN)₂SbCl₅ singlecrystals also remained unchanged. It should be noted that (PPN)₂SbCl₅also exhibited an excellent ambient stability. Single crystals could bekept in the solid state under ambient conditions for two years withlittle-to-no change of PLQE (FIG. 9A), i.e. the PLQE was 98.1% for fresh(PPN)₂SbCl₅ and 97.4% for the same sample after two years' storage. Thehigh stability of (PPN)₂SbCl₅ could be attributed to the formation of 0Dcrystal structure, in which bulky PPN⁺ can dynamically stabilized theSbCl₅ ²⁻ pyramids and protected them from outside environment. Thethermostability of (PPN)₂SbCl₅ crystals was characterized by employingthermogravimetric analysis (TGA in FIG. 9B). The thermal decompositiontemperature was measured at more than 300° C., demonstrating highthermostability of (PPN)₂SbCl₅ single crystals. All these featuressuggested the great potential of practical application of this 0Dorganic metal halide hybrid.

This example demonstrated the development of a novel lead-free X-rayscintillation material, (PPN)₂SbCl₅, which could be prepared via afacile solution process to from single crystals with the size of severalmillimeters. This organic metal halide hybrid adopted a typical 0Dstructure at the molecular level, with isolated SbCl₅ ⁻ anions ionicallybonded to surrounding organic cations PPN⁺. Optical spectroscopicstudies showed that (PPN)₂SbCl₅ had photo absorption in UV region andexhibited excitation dependent dual-band emissions from both organic andinorganic components. When excited with X-rays, the crystals displayedbright salmon pink luminescence and gave a high scintillation lightyield of 49500 ph MeV⁻¹. The response of (PPN)₂SbCl₅ scintillatordisplayed a well linearity at a large range of X-ray dose rate andprovided a low detection limit. Moreover, (PPN)₂SbCl₅ single crystalsexhibited remarkable irradiation, storage, and thermal stabilities. Thisexample suggested a new way to develop low-cost eco-friendly highperformance X-ray scintillators.

Growth of (PPN)₂SbCl₅ and PPNCl single crystals: PPNCl (1.14 mmol) andSbCl₃ (0.57 mmol) were mixed at 2:1 molar ratio and dissolved in 4 mLDCM to form a clear precursor solution. (PPN)₂SbCl₅ single crystals wereprepared by injecting 0.9 mL Et₂O to 0.5 mL as-prepared precursorsolution at room temperature in the N₂-filled glovebox and stood forovernight. The large light color crystals were washed with Et₂O anddried under reduced pressure. The preparation of PPNCl single crystalsfollows above procedures without adding SbCl₃.

Characterization: Single crystal X-ray diffraction (SCXRD) data of(PPN)₂SbCl₅ was collected by using a Rigaku XtaLAB Synergy-S singlecrystal X-ray diffractometer with Mo Kα radiation. The crystal wasmounted in a cryoloop under Paratone-N oil and cooled to 150 K with anOxford Cryosystem 800. A crystallographic information file (CIF) of(PPN)₂SbCl₅ was deposited with CCDC (No. 1983725). Powder XRD spectrumof (PPN)₂SbCl₅ was measured on a Rigaku SmartLab with copper X-ray tuberadiation at a voltage of 40 kV and 40 mA. Simulated XRD pattern of(PPN)₂SbCl₅ was calculated by Mercury software based on itscrystallographic information file (CIF). Thermogravimetric analysis(TGA) was measured by using a TA Instruments TGA 550 system. The sampleswere heated from room temperature to 700° C. at a rate of 20° C.·min⁻¹in an argon atmosphere. UV-Vis absorption spectrum was carried out usinga CARY 5000 UV-Vis NIR spectrophotometer (Agilent Technologies).

Excitation, steady-state photoluminescence (PL), and Time-resolved PL(TRPL) spectra of (PPN)₂SbCl₅ were measured on an Edinburgh FS5spectrofluorometer (Edinburgh Instruments). For TRPL measurement, theexcitation was provided by an Edinburgh EPLED-365 picosecond pulsedlight emitting diode laser. The decay lifetime was calculated bymonoexponential function y=A₁×exp(−x/τ₁)+y₀. The PL quantum efficiencies(PLQEs) were acquired by using a Hamamatsu Quantaurus-QY Spectrometerequipped with a 150 W xenon lamp, calibrated integrating sphere. ThePLQEs were calculated by the equation: η_(QE)=I_(S)(E_(R)−E_(S)), inwhich I_(S) represented the luminescence emission spectrum of sample,E_(R) was the spectrum of the excitation light from the empty integratedsphere, and E_(S) was the excitation spectrum for exciting the sample.Radioluminescence spectra were measured with an Edinburgh FS5spectrofluorometer equipped with a 4 watts Mini-X2 X-ray tube (AMPTEK,Inc.). The dose rate of the X-ray tube under different power wasdetected by a Victoreen 450P-SI chamber survey radiation meter. Thedetection limit was derived as the dose rate when the signal-to-noiseratio was 3. Cerium doped lutetium based scintillator(Lu_(1.8)Y_(0.2)SiO₅:Ce, LYSO) was purchased from Jiaxing AOSITEPhotonics Technology Co., Ltd. and measured under the same conditionswith (PPN)₂SbCl₅.

1. A method for X-ray scintillation, the method comprising: irradiatinga metal halide hybrid with high-energy radiation to convert thehigh-energy radiation to at least one of near ultraviolet light orvisible light.
 2. The method of claim 1, wherein the metal halide hybridhas a 0D structure.
 3. The method of claim 1, wherein— (i) the metalhalide hybrid has a first PLQE measured within one week of the metalhalide hybrid's creation, (ii) a second PLQE measured after the metalhalide hybrid is stored at ambient conditions for at least one yearfollowing the metal halide hybrid's creation, and (iii) the second PLQEis no more than 3 percentage points less than the first PLQE.
 4. Themethod of claim 1, wherein the metal halide hybrid exhibits (i) a lightyield of about 70,000 photons/MeV to about 90,000 photons/MeV, (ii) adetection limit of about 50 nGy/s to about 500 nGy/s, or (iii) acombination thereof.
 5. The method of claim 1, wherein the metal halidehybrid is in the form of one or more discrete crystals.
 6. The method ofclaim 1, wherein each of the one or more discrete crystals has a largestdimension of about 1 mm to about 10 mm.
 7. The method of claim 1,wherein the metal halide hybrid is dispersed in a matrix material. 8.The method of claim 7, wherein the metal halide hybrid is in the form ofa powder.
 9. The method of claim 7, wherein the matrix materialcomprises a polymer.
 10. The method of claim 9, wherein the polymercomprises polydimethylsiloxane.
 11. The method of claim 7, wherein thematrix material is in the form of a film.
 12. (canceled)
 13. The methodof claim 11, wherein the film comprises a polymeric three-dimensionalmicrostructured film. 14-15. (canceled)
 16. A device comprising: anelectronic substrate; an imaging chip; a fiber-optic face plate, whereinthe imaging chip is arranged between the electronic substrate and thefiber-optic face plate; and a scintillator screen comprising a metalhalide hybrid, wherein the fiber-optic face plate is arranged betweenthe imaging chip and the scintillator screen. 17-22. (canceled)
 23. Themethod of claim 1, wherein the metal halide hybrid comprises an organicmetal halide hybrid or an organic metal mixed halide hybrid. 24.(canceled)
 25. The method of claim 1, wherein the metal halide hybridcomprises an inorganic metal halide hybrid or an inorganic metal mixedhalide hybrid.
 26. (canceled)
 27. The method of claim 1, wherein themetal halide hybrid comprises an organic-inorganic metal halide hybrid.28-32. (canceled)
 33. The method of claim 1, wherein the metal halidehybrid comprises an organic antimony halide comprising: a crystalaccording to Formula (I)—R₂SbX₅  Formula (I), wherein X is a halide, and wherein R is an organicammonium cation.
 34. The method of claim 1, wherein the metal halidehybrid comprises an organic manganese (II) halide hybrid comprising— acrystal according to Formula (III)—R′MnX₄  Formula (III), wherein X is a halide, and R′ is an organicphosphonium cation.
 35. An organic antimony halide comprising: a crystalaccording to Formula (I)—R₂SbX₅  Formula (I), wherein X is a halide, and wherein R is an organicammonium cation. 36-45. (canceled)
 46. A scintillator screen comprisingthe organic antimony halide of claim
 35. 47-55. (canceled)